WO2011075804A1 - Piston ring - Google Patents

Piston ring Download PDF

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Publication number
WO2011075804A1
WO2011075804A1 PCT/BR2010/000428 BR2010000428W WO2011075804A1 WO 2011075804 A1 WO2011075804 A1 WO 2011075804A1 BR 2010000428 W BR2010000428 W BR 2010000428W WO 2011075804 A1 WO2011075804 A1 WO 2011075804A1
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WO
WIPO (PCT)
Prior art keywords
layer
coating
fact
ring according
chromium
Prior art date
Application number
PCT/BR2010/000428
Other languages
French (fr)
Portuguese (pt)
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WO2011075804A8 (en
Inventor
Juliano Avelor Araujo
Original Assignee
Malhe Metal Leve S/A
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Malhe Metal Leve S/A filed Critical Malhe Metal Leve S/A
Priority to CN201080064399XA priority Critical patent/CN102869906A/en
Priority to EP10812838A priority patent/EP2518373A1/en
Priority to JP2012545028A priority patent/JP2013515213A/en
Priority to US13/518,300 priority patent/US20130221621A1/en
Publication of WO2011075804A1 publication Critical patent/WO2011075804A1/en
Publication of WO2011075804A8 publication Critical patent/WO2011075804A8/en

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon

Definitions

  • the present invention relates to a piston ring, in particular for use in internal combustion engines or miscellaneous compressors, provided with a plurality of alternating coating layers formed predominantly of metal and ceramic. As a result, the ring has excellent abrasion and erosion resistance properties. Description of the prior art
  • Internal combustion engines are basically made up of two main parts: an engine block (where one or more cylinders are located and the crankshaft assembly or crankshaft assembly), to which one or more cylinder heads are associated.
  • the crankshaft assembly is composed of pistons, connecting rods and crankshaft, emphasizing that the piston is a cylindrical part, usually of an aluminum alloy that moves inside the cylinder.
  • the clearance between the upper face of the piston, the cylinder wall and the base of the cylinder head corresponds to the combustion chamber, and in diesel engines the combustion chamber (s) is generally defined. primarily provided by cavity (s) provided in the piston head (s).
  • the engine converts the chemical energy produced by combustion of the mixture (fuel and air) into mechanical energy capable of imprinting movement on the wheels.
  • rings are required to provide a sliding seal between the outer edge of the piston and the inner wall of the cylinder.
  • the piston When displacing the piston inside the cylinder, the piston should adhere fully to the cylinder walls to prevent the air / fuel mixture and exhaust gases leaking from the combustion chamber into the oil pan during compression and combustion and further preventing crankcase oil from entering the combustion zone. Due to the high friction such a solution would cause, the solution found was to design a small clearance between the piston and the cylinder inner walls, placing one or more rings around the piston to ensure the necessary insulation. This clearance also provides space for the piston to expand with engine heating without adhering to the surrounding cylinder walls, which would prevent piston movement.
  • piston rings notably compression rings
  • piston rings are formed of a metal base to which at least one coating layer is applied which contacts the cylinder wall (to the working surface of the ring).
  • the role of the coating layer is of the most importance because it seeks to give the ring properties of low slip friction, high peeling resistance, hardness and toughness. However, many of these properties are antagonistic and an increase in one of them means a loss of performance in another, so the type of liner to be used will be chosen depending on the engine operating profile and the stresses to which the rings will be subjected. during its lifetime.
  • a first prior art is represented by US Patent 5,316,321, which relates to an internal combustion engine piston ring made from a titanium alloy whose sliding outer surface is coated with a hard film employing a Physical Vapor Deposition (PVD) for this deposition.
  • PVD Physical Vapor Deposition
  • US 5,316,321 further describes the use of one or more types of films for piston ring coating, especially TiN (Titanium Nitride) and CrN (Chromium Nitride).
  • US 5,820,131 discloses a piston ring having a coating formed of a single layer C CN film or a mixture of thick Cr 2 N and CrN from 3pm to 30pm and a percentage by weight of nitrogen between 11% and 17%.
  • the coating layer is applied by the PVD process and its hardness ranges between 1300 HV and 2000 HV.
  • US 5,618,590 relates to a piston ring coated with a film of one or more layers applied by a cathodic arc deposition process.
  • US 5,618,590 further describes that the applied process is capable of forming a first layer making use of a metal (such as cobalt, nickel or molybdenum) unable to form a carbide or nitride and a second layer making use of a metal (such as titanium, vanadium, chromium, iron, zirconium, niobium, tungsten or silicon) capable of forming a carbide or nitride.
  • a metal such as cobalt, nickel or molybdenum
  • European patent EP 0.707.092 relates to a piston ring with a coating layer formed of a mixture of chromium. metallic and chromium nitride, applied by PVD. The document further describes that the nitrogen concentration has a gradual increase from the metal base to the outside of the ring.
  • US Patent 5,601,293 discloses a piston ring with a single ternary coating comprised of molybdenum nitride, chromium nitride and a percentage of nitrogen by weight of between 4% and 22%.
  • the coating layer is applied by the PVD process and its hardness ranges between 1400 HV and 2600 HV.
  • Japanese patent JP 6.293954 refers to a single layer piston ring formed of at least chromium nitride by the PVD process.
  • the crystal of the formed layer further has a columnar shape extending from the substrate surface to the surface of the nitrided layer.
  • Japanese patent document JP 6.248.425 describes a piston ring lined with a layer formed by CrN and / or Cr 2 N, with a thickness ranging from 1 to 60 ⁇ . As in the previous document, this document also describes that the formed layer consists of a crystal whose columnar shape extends from the surface of the substrate to the surface of the nitrided layer.
  • Japanese Patent Application JP 2006 316912 discloses a piston ring whose metal base may be of a steel, aluminum or titanium alloy and which uses a PVD process to create a low roughness surface film.
  • the document further describes that the film on the substrate surface may consist of combinations of Ti and / or Cr, C, N and O.
  • the piston ring object of the present invention by presenting an innovative constitution, furthers the properties presented by the coating layer.
  • a multilayer coating is proposed, composed of a plurality of consecutive Ceramic / Metallic layers, alternating in major composition chromium nitride (CrN) and metallic chromium (Cr).
  • each compound has the best properties of enhanced as the ductile metal layers (Cr) facilitate the accommodation of the hard ceramic layers (CrN), the latter giving the coating a higher hardness and wear resistance, while a higher layer plasticity formed by metallic chrome contributes to a considerable reduction in internal stress values, enabling greater thickness of the coatings.
  • Cr ductile metal layers
  • CrN hard ceramic layers
  • the coating developed here gives the piston ring a higher wear resistance, lower modulus of elasticity and, concomitantly, a considerable reduction in internal stress values, reducing the occurrence of cracks in the coating and the consequent scaling when compared to the previous techniques, notably those that make use of chrome nitride coatings.
  • the present invention is directed to a piston ring, particularly for the use of an internal combustion engine or compressor, provided with a coating based on the Ceramic / Metal multilayer concept.
  • the present invention is also directed to a piston ring particularly suited for use in combustion engines.
  • compressors comprising at least one metal base to which a coating of metallic chromium and chromium nitride is applied by the physical vapor deposition process to concomitantly exhibit the antagonistic properties of hardness, wear resistance , ductility and reduction of elastic modulus and internal stress.
  • the present invention is directed to a piston ring, particularly for use with an internal combustion engine or compressor, provided with a plurality of CrN / Cr ceramic / metal coating layers having a thickness compared to the coating thickness. of the prior art rings with chromium nitride coating.
  • the present invention is directed to the process of applying a plurality of ceramic / metal coating layers to a metal piston ring body in a single application step by varying the nitrogen gas pressure in the process. physical vapor deposition.
  • a piston ring particularly ideal for use in internal combustion engines or compressors, comprising at least one metal base to which a coating which is applied by the physical vapor deposition (PVD) process is applied.
  • PVD physical vapor deposition
  • Figure 1 is a schematic cross-sectional view of the piston ring object of the present invention mounted on a piston groove and in friction with the wall of a cylinder.
  • Figure 2 is an enlarged metallographic photograph of the piston ring cross-section object of the present invention, allowing the visualization of the metal base and the respective multilayer coating.
  • the piston ring 1 object of the present invention differs from the present ones, essentially due to the advantageous and innovative characteristics of its coating 3.
  • ring 1 is preferably a compression ring for use in 4-stroke internal combustion engines, and ring 1 may well have other embodiments, such as an oil scraper ring, a ring applied on a piston compressor, a 2-stroke engine ring or even any other possible embodiment wherein
  • Ring 1 has a coating 3 with the innovative characteristics set forth herein.
  • the present invention comprises at least one metal base 2 to which a physical vapor deposition (PVD) process is applied to a coating 3 provided with a plurality of layers (5,5 ') alternating between a metal layer 5 and a 5 'ceramic layer.
  • PVD physical vapor deposition
  • Coating 3 is composed of 5,5 'metal / ceramic multilayers arranged to form at least two periodicities P where each periodicity is formed by at least one layer of metallic chrome 5 and at least one layer of ceramic chrome 5'. adjoining.
  • the base 2 is composed of any metal material suitable for its formation and may have a cross-section of various shapes, depending on the characteristics of the ring 1 and the working conditions under which it will operate.
  • any ferrous alloy suitable for the composition of base 2 is preferably used, and it is clearly possible to make use of other materials if there is interest and technical feasibility.
  • base 2 is comprised of steel with 10 to 17% Chromium, commonly known as stainless steel.
  • Chrome 2 Metallic / Ceramic Coating 3 is applied to base 2 which gives the ring 1 properties of higher wear resistance, lower elastic modulus and, concomitantly, a considerable reduction in internal stress values, reducing the occurrence of cracks in the coating and the consequent scaling as compared to the prior art, particularly those using chromium nitride monolayer coatings.
  • cladding 3 comprises a plurality of 5.5 'Chrome-based Metal / Ceramic layers arranged to form a P-periodicity. Therefore, P-periodicity comprises at least two adjacent 5.5' layers, which must be of different constitution, that is, one layer 5 has a preponderant metallic phase and another layer 5 'has a preponderant ceramic phase. Thus, the coating 3 will have at least four layers 5.5 '.
  • One of the qualities of the metallic layer 5 that makes up the coating 3 comprises chromium (Cr) in its metallic form (illustrated as the lighter layers in figure 2), whose main mechanical characteristic is greater ductility, which facilitates the accommodation - 5 'hard ceramic layers.
  • Cr chromium
  • the ceramic layer 5 'comprises chromium nitride (shown as the darker layers in figure 2), preferably in the form of CrN (although, of course, there may be a reduced percentage of Cr 2 N and / or other compounds. / elements in its composition), having as its main mechanical characteristic the high hardness. It is of particular importance to note that 5 'ceramic layer chromium nitride may also present predominantly with the Cr 2 N phase rather than the CrN phase.
  • the periodicity P has at least one metal layer 5 composed predominantly of Cr and one ceramic layer 5 'composed predominantly of CrN or Cr 2 N.
  • the metal layer 5 should be positioned adjacent to the ceramic layer 5 'or vice versa. This ensures that the 5.5 'coating layers are interspersed without repetition.
  • any of the 5,5 'layers may be deposited on the surface of the base 2, therefore it is possible to deposit as the first layer on the base 2 both the metallic layer 5 and the ceramic layer 5'.
  • a distinct layer will alternate, ie if the first layer to be deposited on the surface of the base 2 is the ceramic layer 5 'then the metallic layer 5 will be followed, or vice versa, and so on.
  • a ring 1 may be designed according to the teachings of the present invention in which there may exceptionally be two adjacent layers of equal quality, depending on the strength and ductility qualities desired to be imparted to the coating 3.
  • the coating 3 of the preferred embodiment of ring 1 comprises nine 5.5 'metal / ceramic layers, where the qualities of the 5.5' layers of coating 3 are interspersed without repetition.
  • the 5.5 'layers may comprise one or more additional chemical elements, in varying proportions and calculated as a function of the desired mechanical property. Even if some mixing occurs in the individual 5.5 'layers, it is expected to achieve the same degree of advantages, that is, the aforementioned advantages of the present invention with a 5.5' multilayer coating 3 where one layer has predominance are also expected. ceramic and the subsequent metallic predominance layer.
  • Such possible chemical elements may be present in at least one of the 5.5 'layers, some of them or in all, depending on the mechanical properties of the coating desired, provided that the characteristics of a metal / ceramic multi-layer coating are maintained.
  • the coating 3 of the present invention obtained really superior results in all measured characteristics. Therefore, an increase in the values for antagonistic properties is confirmed, a fact which really proves the success of the coating 3 of the present invention.
  • the present invention when compared with the typical CrN monolayer coating, achieves a significantly lower value for the modulus of elasticity and a significant reduction in internal stress (substantially 3.5 times less).
  • Figure 2 shows a coating 3 with two distinct 5.5 'layers where the difference is basically in the chromium content, therefore cohesive boundaries between the 5.5' Metallic / Ceramic layers are expected in order to ensure adhesion. between the 5,5 'layers thus avoiding the propagation of cracks in its interface.
  • the reduction in internal stress values translates into a much greater resistance to the scaling phenomenon, in which small portions of the The dressings are bare due to the occurrence of microcracks caused by the accumulation of tensions and low ductility.
  • the major technical drawback is that scaling tends to occur in certain parts of the ring, while in other parts the coating remains intact or undamaged even at the end of part life.
  • the 5.5 'Multilayer Metal / Ceramic coating 3 of the present invention of preferred chrome metal and chromium nitride structure (in the CrN or Cr 2 N phase), provides a clear improvement in the compromise between higher the ability to absorb stress concomitantly with greater resistance to surface crack propagation due to improved external shear stress resistance characteristics, which results in superior performance of the coating 3 of the present invention for piston rings 1 with respect to cohesive adhesion (delamination resistance).
  • the deposition process applied in the present invention is a physical vapor deposition (PVD) process, preferably by cathode arc, or PV-Arc which is a PVD technique where an electric arc is used to vaporize material from a cathode. target.
  • PVD physical vapor deposition
  • the vaporized material then condenses on a substrate and forms a thin film.
  • gas pressure control eg nitro- used
  • gas pressure control enables the production of the 5.5 'layers sequentially, with the chromium nitride layers having a percentage of nitrogen atoms of between 22% and 25% by weight, whereas in the chromium metal layers they have substantially 0% Nitrogen atoms.
  • high bombardment rates are applied through turbo pumps.
  • the thickness and periodicity values are considered quite stable throughout the coating (see figure 2), however, the 5.5 'layers follow the base 2 deformities, resulting in the visible shapes of figure 2.
  • the highest hardness is obtained with the chromium nitride composition and the highest ductility is achieved with the use of metal chromium.
  • the combination of these two compositions in the form of the 5,5 'layers brings surprising advantages, notably in the benefit presented to the coating 3 as a whole for its greater internal stress absorption capacity.
  • the more ductile metallic chrome layers 5 absorb stress and deform, thereby decreasing the deformation forces to which the stiffer chrome nitride 5 'layers are subjected, providing a lower tendency for microcracks to appear on them.
  • the result is a considerable increase in ring performance 1.
  • the preferred embodiment of ring 1, illustrated in Figure 2 has a surface hardness of the order of 1000 to 2000 HV, preferably around 1350 HV, with an internal stress of about -310 N / mm 2 .
  • the thickness of the coating (3) is in the range of about 10 to 60 microns, i.e. very low thickness ( ⁇ .
  • an adhesion layer composed of chromium, nickel or cobalt may be provided positioned between base 2 and coating 3.
  • the coating 3 is applied over the entire outer surface of ring 1, but nothing prevents it from being applied in certain parts, partially removed or any other coating quality applied thereon.
  • a piston ring thus configured remains within the protection scope of the claims.

Abstract

The present invention relates to a piston ring designed in particular for use in internal combustion engines or compressors, and comprising at least one metallic base (2) to which is applied by physical vapour deposition (PVD) a multilayer coating (3) with a periodic repetition (P) of at least one first layer (5) and at least one second layer (5') adjacent to the first, where a first layer (5) is mainly composed of chromium metal (5) and a second layer is mainly composed of chromium ceramic (5').

Description

Relatório Descritivo da Patente de Invenção para "ANEL DE PISTÃO".  Patent Descriptive Report for "PISTON RING".
A presente invenção refere-se a um anel de pistão, em especial para utilização em motores de combustão interna ou compressores diversos, dotado de uma pluralidade de camadas de revestimento alternadas forma- das preponderantemente por um metal e um cerâmico. Como resultado, o anel apresenta excelentes propriedades de resistência à abrasão e erosão. Descrição do estado da técnica  The present invention relates to a piston ring, in particular for use in internal combustion engines or miscellaneous compressors, provided with a plurality of alternating coating layers formed predominantly of metal and ceramic. As a result, the ring has excellent abrasion and erosion resistance properties. Description of the prior art
Os motores de combustão interna são constituídos basicamente por duas partes principais: um bloco de motor (onde estão localizados um ou mais cilindros e o conjunto da árvore de manivelas ou conjunto do vira- brequim), ao qual são associados um ou mais cabeçotes. O conjunto da árvore de manivelas é composto por pistões, bielas e pelo virabrequim, realçando que o pistão é uma peça cilíndrica, usualmente de uma liga metálica de alumínio, que se move no interior do cilindro.  Internal combustion engines are basically made up of two main parts: an engine block (where one or more cylinders are located and the crankshaft assembly or crankshaft assembly), to which one or more cylinder heads are associated. The crankshaft assembly is composed of pistons, connecting rods and crankshaft, emphasizing that the piston is a cylindrical part, usually of an aluminum alloy that moves inside the cylinder.
O espaço definido entre a face superior do pistão, a parede do cilindro e a base do cabeçote corresponde à câmara de combustão, sendo que nos motores Diesel, em geral, a(s) câmara(s) de combustão é(são) defi- nida(s) primordialmente por cavidade(s) provida(s) na(s) cabeça(s) do(s) pistão(ões).  The clearance between the upper face of the piston, the cylinder wall and the base of the cylinder head corresponds to the combustion chamber, and in diesel engines the combustion chamber (s) is generally defined. primarily provided by cavity (s) provided in the piston head (s).
No interior da(s) câmara(s) de combustão, o motor converte a energia química produzida pela combustão da mistura (combustível e ar) em energia mecânica capaz de imprimir movimento às rodas.  Inside the combustion chamber (s), the engine converts the chemical energy produced by combustion of the mixture (fuel and air) into mechanical energy capable of imprinting movement on the wheels.
Com a finalidade de impedir que a mistura de ar/combustível e que os gases de escapamento vazem da câmara de combustão para dentro do cárter de óleo durante a compressão e a combustão e ainda impedir que o óleo do cárter passe para dentro da zona de combustão, faz-se necessária utilização de anéis para providenciar uma vedação deslizante entre a borda externa do pistão e a parede interna do cilindro.  In order to prevent the air / fuel mixture and exhaust gases from leaking from the combustion chamber into the oil pan during compression and combustion and further prevent the crankcase oil from entering the combustion zone , rings are required to provide a sliding seal between the outer edge of the piston and the inner wall of the cylinder.
Durante o deslocamento do pistão no interior do cilindro, o pis- tão deveria aderir totalmente às paredes do cilindro de forma a impedir que a mistura de ar/combustível e que os gases de escapamento vazassem da câmara de combustão para dentro do cárter de óleo durante a compressão e a combustão e ainda impedir que o óleo do cárter passe para dentro da zona de combustão. Em função do elevado atrito que tal solução provocaria, a solução encontrada foi projetar uma pequena folga entre o pistão e as paredes internas do cilindro, colocando um ou mais anéis em volta do pistão de modo a assegurar o isolamento necessário. Esta folga permite ainda garantir espaço para que o pistão se possa dilatar com o aquecimento do motor sem aderir às paredes do cilindro envolvente, situação que impediria o movimento do pistão. When displacing the piston inside the cylinder, the piston should adhere fully to the cylinder walls to prevent the air / fuel mixture and exhaust gases leaking from the combustion chamber into the oil pan during compression and combustion and further preventing crankcase oil from entering the combustion zone. Due to the high friction such a solution would cause, the solution found was to design a small clearance between the piston and the cylinder inner walls, placing one or more rings around the piston to ensure the necessary insulation. This clearance also provides space for the piston to expand with engine heating without adhering to the surrounding cylinder walls, which would prevent piston movement.
Usualmente, os motores de 4 tempos mais modernos utilizam três anéis em cada pistão, sendo dois anéis de compressão e um anel de óleo. Os dois anéis situados mais perto da cabeça do pistão são chamados segmentos de compressão e têm por finalidade assegurar que não haja fuga da mistura gasosa para o interior do cárter no momento em que o pistão efe- tua o seu movimento de compressão. Na posição mais afastada da cabeça do pistão situa-se o chamado anel de óleo cujo objetivo é, quando da sua movimentação (notadamente a movimentação afastando-se do cabeçote), raspar o excesso de óleo da parede do cilindro e retirar o excesso, contro- lando a espessura do 'filme' de óleo e impedindo sua queima indevida.  Most modern 4-stroke engines usually use three rings on each piston, two compression rings and one oil ring. The two rings closest to the piston head are called compression segments and are intended to ensure that the gas mixture does not leak into the crankcase at the moment the piston makes its compression movement. At the furthest position from the piston head is the so-called oil ring, the purpose of which is to scrape excess oil from the cylinder wall and remove excess oil when it is moved (notably moving away from the cylinder head). - reducing the thickness of the oil 'film' and preventing its improper burning.
Em geral, os anéis de pistão, notadamente os anéis de compressão, são formados por uma base metálica à qual é aplicada pelo menos uma camada de revestimento, que entra em contato com a parede do cilindro (à superfície de trabalho do anel).  In general, piston rings, notably compression rings, are formed of a metal base to which at least one coating layer is applied which contacts the cylinder wall (to the working surface of the ring).
O papel da camada de revestimento é dos mais importantes, porque busca conferir ao anel propriedades de baixo atrito de deslizamento, grande resistência à escamação, dureza e tenacidade. Porém, muitas dessas propriedades são antagónicas e um acréscimo em uma delas significa uma perda de desempenho em outra, pelo que o tipo de revestimento a ser utilizado vai ser escolhido em função do perfil de funcionamento do motor e aos esforços aos quais os anéis serão submetidos durante sua vida útil.  The role of the coating layer is of the most importance because it seeks to give the ring properties of low slip friction, high peeling resistance, hardness and toughness. However, many of these properties are antagonistic and an increase in one of them means a loss of performance in another, so the type of liner to be used will be chosen depending on the engine operating profile and the stresses to which the rings will be subjected. during its lifetime.
Uma série de revestimentos sofisticados foram propostos por aqueles entendidos no assunto, cada qual buscando incrementar as propriedades desejadas. Porém, nenhum dos revestimentos propostos até o presente momento foi eficiente em aumentar, concomitantemente, as propriedades de absorção de estresse interno, elevada dureza e baixa espessura, o que reduz sobremaneira a ocorrência de escamação ('spalling'). A number of sophisticated coatings have been proposed by those skilled in the subject, each seeking to increase the desired properties. However, none of the coatings proposed to date have been effective in concomitantly increasing the properties of internal stress absorption, high hardness and low thickness, which greatly reduces the occurrence of spalling.
Uma primeira técnica anterior está representada pela patente US 5.316.321 , que refere-se a um anel de pistão para motor de combustão interna fabricado a partir de uma liga de titânio, cuja superfície externa de deslizamento é revestida por um filme duro, empregando processo de depo- sição física de vapor, do inglês "PVD" (Physical Vapour Deposition) para essa deposição.  A first prior art is represented by US Patent 5,316,321, which relates to an internal combustion engine piston ring made from a titanium alloy whose sliding outer surface is coated with a hard film employing a Physical Vapor Deposition (PVD) for this deposition.
O documento US 5.316.321 descreve ainda o uso de um ou mais tipos de filmes para o revestimento do anel de pistão, especialmente o TiN (Nitreto de Titânio) e o CrN (Nitreto de Cromo).  US 5,316,321 further describes the use of one or more types of films for piston ring coating, especially TiN (Titanium Nitride) and CrN (Chromium Nitride).
Uma segunda técnica anterior desenvolvida está representada pelo caso de patente US 5.820.131 , que revela um anel de pistão dotado de um revestimento formado por um filme de uma única camada de C^N ou uma mistura de Cr2N e CrN, com espessura de 3pm a 30pm e um percentual de nitrogénio, em peso, entre 11% e 17%. A camada de revestimento é aplicada pelo processo de PVD e sua dureza oscila entre 1300 HV e 2000 HV. A second developed prior art is represented by US 5,820,131, which discloses a piston ring having a coating formed of a single layer C CN film or a mixture of thick Cr 2 N and CrN from 3pm to 30pm and a percentage by weight of nitrogen between 11% and 17%. The coating layer is applied by the PVD process and its hardness ranges between 1300 HV and 2000 HV.
A patente US 5.618.590 refere-se a um anel de pistão revestido por um filme de uma ou mais camadas aplicadas por um processo de deposição por arco catódico.  US 5,618,590 relates to a piston ring coated with a film of one or more layers applied by a cathodic arc deposition process.
O documento US 5.618.590 descreve ainda que o processo a- plicado é capaz de formar uma primeira camada que faz uso de um metal (tal como o cobalto, níquel ou molibdênio) incapaz de formar um carboneto ou nitreto e uma segunda camada que faz uso de um metal (tal como titânio, vanádio, cromo, ferro, zircônio, nióbio, tungsténio ou silício) capaz de formar um carboneto ou nitreto.  US 5,618,590 further describes that the applied process is capable of forming a first layer making use of a metal (such as cobalt, nickel or molybdenum) unable to form a carbide or nitride and a second layer making use of a metal (such as titanium, vanadium, chromium, iron, zirconium, niobium, tungsten or silicon) capable of forming a carbide or nitride.
A patente européia EP 0.707.092 refere-se a um anel de pistão dotado de uma camada de revestimento formada por uma mistura de cromo metálico e nitreto de cromo, aplicado por PVD. O documento descreve ainda que a concentração de nitrogénio tem um aumento gradativo desde a base metálica até ao exterior do anel. European patent EP 0.707.092 relates to a piston ring with a coating layer formed of a mixture of chromium. metallic and chromium nitride, applied by PVD. The document further describes that the nitrogen concentration has a gradual increase from the metal base to the outside of the ring.
Outra técnica anterior está representada pela patente US 5.601.293, que revela um anel de pistão dotado de um revestimento formado por uma única camada ternária compreendida por nitreto de molibdênio, nitreto de cromo e um percentual de nitrogénio, em peso, entre 4% e 22%. A camada de revestimento é aplicada pelo processo de PVD e sua dureza oscila entre 1400 HV e 2600 HV.  Another prior art is represented by US Patent 5,601,293, which discloses a piston ring with a single ternary coating comprised of molybdenum nitride, chromium nitride and a percentage of nitrogen by weight of between 4% and 22%. The coating layer is applied by the PVD process and its hardness ranges between 1400 HV and 2600 HV.
O patente japonesa JP 6.293.954 faz referência a um anel de pistão revestido por uma única camada formada por pelo menos nitreto de cromo pelo processo PVD. O cristal da camada formada apresenta ainda uma forma colunar que se estende desde a superfície do substrato até à superfície da camada nitretada.  Japanese patent JP 6.293954 refers to a single layer piston ring formed of at least chromium nitride by the PVD process. The crystal of the formed layer further has a columnar shape extending from the substrate surface to the surface of the nitrided layer.
O documento de patente japonês JP 6.248.425 descreve um anel de pistão revestido por uma camada formada por CrN e/ou Cr2N, com uma espessura que varia de 1 a 60 μιη. Tal como no documento anterior, este documento também descreve que a camada formada consiste em um cristal cuja forma colunar se estende desde a superfície do substrato até à superfície da camada nitretada. Japanese patent document JP 6.248.425 describes a piston ring lined with a layer formed by CrN and / or Cr 2 N, with a thickness ranging from 1 to 60 μιη. As in the previous document, this document also describes that the formed layer consists of a crystal whose columnar shape extends from the surface of the substrate to the surface of the nitrided layer.
O pedido de patente japonês JP 2006 316912 revela um anel de pistão cuja base metálica pode ser de uma liga de aço, alumínio ou titânio e que faz uso de um processo PVD para criar um filme superficial com baixa rugosidade. O documento descreve ainda que o filme na superfície do subs- trato pode ser constituído por combinações de Ti e/ou Cr, C, N e O.  Japanese Patent Application JP 2006 316912 discloses a piston ring whose metal base may be of a steel, aluminum or titanium alloy and which uses a PVD process to create a low roughness surface film. The document further describes that the film on the substrate surface may consist of combinations of Ti and / or Cr, C, N and O.
Por fim, uma última técnica anterior representativa pode ser encontrada na patente US 6.631.907, que se refere a um anel de pistão dotado de uma camada de revestimento composta por CrN ou Cr2N, ou ainda um mistura de nitretos, aplicada por PVD. O documento contempla ainda a aplicação de uma mistura de CrN com Cr2N e Cr metálico, e discorre fartamente acerca de percentuais em peso dos componentes. Finally, a last representative prior art can be found in US 6,631,907, which relates to a piston ring having a coating layer composed of CrN or Cr 2 N, or a PVD-applied nitride mixture . The document further contemplates the application of a mixture of CrN with Cr 2 N and metallic Cr, and abundantly discusses by weight percentages of the components.
Chama-se, portanto, a atenção para o fato de nenhuma das tec- nicas anteriores fazer referência à formação de um revestimento multicama- das (ou, para os técnicos no assunto, πΐίΐΙΜθγβή, formado alternadamente por camadas cerâmicas/metálicas à base de cromo. Attention is therefore drawn to the fact that none of the Formerly, reference should be made to the formation of a multilayer coating (or, for those skilled in the art, πΐίΐΙΜθγβή, formed alternately of chrome-based ceramic / metal layers.
Por outras palavras, o anel de pistão objeto da presente inven- ção, ao apresentar uma constituição inovadora, leva adiante as propriedades apresentadas pela camada de revestimento. Pela primeira vez, é proposto um revestimento multicamadas, composto por uma pluralidade de camadas consecutivas Cerâmica/Metálica, alternando em composição majoritária nitreto de cromo (CrN) e cromo metálico (Cr).  In other words, the piston ring object of the present invention, by presenting an innovative constitution, furthers the properties presented by the coating layer. For the first time, a multilayer coating is proposed, composed of a plurality of consecutive Ceramic / Metallic layers, alternating in major composition chromium nitride (CrN) and metallic chromium (Cr).
Como resultado obtém-se um filme com o melhor dos dois componentes, pelo fato de apresentar as propriedades desejáveis de cada camada cerâmica e metálica, sem potencializar os pontos fracos de cada qual.  As a result, a film with the best of both components is obtained by presenting the desirable properties of each ceramic and metallic layer, without enhancing the weaknesses of each one.
As melhores propriedades de cada composto são potencializadas visto que as camadas metálicas dúcteis (Cr) facilitam a acomodação das duras camadas cerâmicas (CrN), sendo que estas últimas conferem ao revestimento uma maior dureza e resistência ao desgaste, enquanto que a maior plasticidade da camada formada pelo cromo metálico colabora com uma redução considerável nos valores de estresse interno, possibilitando maiores espessuras dos revestimentos.  The best properties of each compound are enhanced as the ductile metal layers (Cr) facilitate the accommodation of the hard ceramic layers (CrN), the latter giving the coating a higher hardness and wear resistance, while a higher layer plasticity formed by metallic chrome contributes to a considerable reduction in internal stress values, enabling greater thickness of the coatings.
O revestimento ora desenvolvido confere ao anel de pistão uma maior resistência ao desgaste, menor modulo de elasticidade e, concomitantemente, uma redução considerável nos valores de estresse interno, reduzindo a ocorrência de trincas no revestimento e a consequente escamação quando comparado com as técnicas anteriores, notadamente aquelas que fazem uso de revestimentos de nitreto de cromo.  The coating developed here gives the piston ring a higher wear resistance, lower modulus of elasticity and, concomitantly, a considerable reduction in internal stress values, reducing the occurrence of cracks in the coating and the consequent scaling when compared to the previous techniques, notably those that make use of chrome nitride coatings.
Objetivos da invenção Objectives of the invention
A presente invenção tem por objetivo um anel de pistão, particularmente para utilização de motor de combustão interna ou compressor, dotado de um revestimento baseado no conceito de multicamadas Cerâmi- ca/Metálica.  The present invention is directed to a piston ring, particularly for the use of an internal combustion engine or compressor, provided with a coating based on the Ceramic / Metal multilayer concept.
A presente invenção tem por objetivo também um anel de pistão, particularmente idealizado para utilização em motores de combustão interna ou compressores, compreendendo pelo menos uma base metálica à qual é aplicado, pelo processo de deposição física de vapor, um revestimento de cromo metálico e de nitreto de cromo, de modo a apresentar concomitantemente as antagónicas propriedades de dureza, resistência ao desgas- te, ductilidade e redução do modulo de elasticidade e do estresse interno. The present invention is also directed to a piston ring particularly suited for use in combustion engines. compressors, comprising at least one metal base to which a coating of metallic chromium and chromium nitride is applied by the physical vapor deposition process to concomitantly exhibit the antagonistic properties of hardness, wear resistance , ductility and reduction of elastic modulus and internal stress.
Ainda, a presente invenção tem por objetivo um anel de pistão, particularmente para utilização de motor de combustão interna ou compressor, dotado de uma multiplicidade de camadas de revestimento cerâmico/metálica CrN/Cr, que apresentem menor espessura se comparadas com a espessura do revestimento dos anéis da técnica anterior com revestimento de nitreto de cromo.  Further, the present invention is directed to a piston ring, particularly for use with an internal combustion engine or compressor, provided with a plurality of CrN / Cr ceramic / metal coating layers having a thickness compared to the coating thickness. of the prior art rings with chromium nitride coating.
Finalmente, a presente invenção tem por objetivo o processo de aplicação de uma multiplicidade de camadas de revestimento cerâmico/metálico em um corpo de anel de pistão metálico, em uma única etapa de aplicação, por meio da variação da pressão do gás nitrogénio no processo de deposição física de vapor.  Finally, the present invention is directed to the process of applying a plurality of ceramic / metal coating layers to a metal piston ring body in a single application step by varying the nitrogen gas pressure in the process. physical vapor deposition.
Breve descrição da invenção Brief Description of the Invention
Os objetos da presente invenção são alcançados por um anel de pistão, particularmente idealizado para utilização em motores de combustão interna ou compressores, compreendendo pelo menos uma base metálica à qual é aplicado, pelo processo de deposição física de vapor (PVD), um revestimento que compreende uma periodicidade, formada por pelo menos uma primeira camada e pelo menos uma segunda camada adjacentes, sendo que a primeira camada é formada preponderantemente por cromo metá- lico e a segunda camada é formada preponderantemente por cromo cerâmico.  The objects of the present invention are achieved by a piston ring, particularly ideal for use in internal combustion engines or compressors, comprising at least one metal base to which a coating which is applied by the physical vapor deposition (PVD) process is applied. comprises a periodicity formed by at least one first layer and at least one adjacent second layer, the first layer being formed predominantly of metal chromium and the second layer being formed predominantly of ceramic chromium.
Descrição resumida dos desenhos  Brief Description of the Drawings
A presente invenção será, a seguir, mais detalhadamente descrita com base em um exemplo de execução representado nos desenhos. As figuras mostram:  The present invention will hereinafter be described in more detail based on an exemplary embodiment shown in the drawings. The figures show:
Figura 1 - é uma vista esquemática em corte transversal do anel de pistão objeto da presente invenção montado no canalete de um pistão e em atrito com a parede de um cilindro. Figure 1 is a schematic cross-sectional view of the piston ring object of the present invention mounted on a piston groove and in friction with the wall of a cylinder.
Figura 2 - é uma fotografia metalográfica ampliada da secção transversal do anel de pistão objeto da presente invenção, permitindo a visualização da base metálica e do revestimento multicamadas respectivo. Descrição detalhada das figuras  Figure 2 is an enlarged metallographic photograph of the piston ring cross-section object of the present invention, allowing the visualization of the metal base and the respective multilayer coating. Detailed Description of the Figures
O anel de pistão 1 objeto da presente invenção difere dos atu- almente existentes, fundamentalmente, pelas vantajosas e inovadoras características de seu revestimento 3.  The piston ring 1 object of the present invention differs from the present ones, essentially due to the advantageous and innovative characteristics of its coating 3.
De realçar que o anel 1 é preferivelmente um anel de compres- são para uso em motores de combustão interna a 4 tempos, sendo que o anel 1 pode muito bem ter outras concretizações, tais como, um anel raspador de óleo, um anel aplicado em um compressor a pistão, um anel de um motor a 2 tempos ou mesmo qualquer outra possível concretização em que Note that ring 1 is preferably a compression ring for use in 4-stroke internal combustion engines, and ring 1 may well have other embodiments, such as an oil scraper ring, a ring applied on a piston compressor, a 2-stroke engine ring or even any other possible embodiment wherein
0 anel 1 apresente um revestimento 3 com as inovadoras características ora definidas. Ring 1 has a coating 3 with the innovative characteristics set forth herein.
Qualquer que seja a configuração preferencial, o anel de pistão Whatever the preferred configuration, the piston ring
1 da presente invenção compreende pelo menos uma base metálica 2, à qual é aplicado, pelo processo de deposição física de vapor (PVD), um revestimento 3 dotado de uma pluralidade de camadas (5,5') alternadas entre uma camada metálica 5 e uma camada cerâmica 5'. 1 of the present invention comprises at least one metal base 2 to which a physical vapor deposition (PVD) process is applied to a coating 3 provided with a plurality of layers (5,5 ') alternating between a metal layer 5 and a 5 'ceramic layer.
O revestimento 3 é composto por multicamadas metálicas/cerâmicas 5,5' arranjadas de modo a formar pelo menos duas periodici- dades P onde cada periodicidade é formada por pelo menos uma camada de cromo metálico 5 e pelo menos uma camada de cromo cerâmico 5' adja- centes.  Coating 3 is composed of 5,5 'metal / ceramic multilayers arranged to form at least two periodicities P where each periodicity is formed by at least one layer of metallic chrome 5 and at least one layer of ceramic chrome 5'. adjoining.
Adicionalmente, a base 2 é composta por qualquer material metálico adequado à sua formação e pode apresentar secção transversal de diversos formatos, em função das características do anel 1 e das condições de trabalho segundo as quais operará. Para tal, é utilizada, de modo prefe- rencial, qualquer liga ferrosa adequada à composição da base 2, sendo claramente possível fazer uso de outros materiais caso haja interesse e viabilidade técnica. Mais preferivelmente, a base 2 é composta por aço com 10 a 17 % de Cromo, habitualmente conhecido como aço inoxidável. Additionally, the base 2 is composed of any metal material suitable for its formation and may have a cross-section of various shapes, depending on the characteristics of the ring 1 and the working conditions under which it will operate. For this purpose, any ferrous alloy suitable for the composition of base 2 is preferably used, and it is clearly possible to make use of other materials if there is interest and technical feasibility. More preferably, base 2 is comprised of steel with 10 to 17% Chromium, commonly known as stainless steel.
À base 2 é aplicado o revestimento 3 Metálico/Cerâmico à base de cromo que confere ao anel 1 propriedades de maior resistência ao desgaste, menor modulo de elasticidade e, concomitantemente, uma redução considerável nos valores de estresse interno, reduzindo a ocorrência de trincas no revestimento e a consequente escamação quando comparado com as técnicas anteriores, nomeadamente aquelas que fazem uso de revestimentos monocamada de nitreto de cromo.  Chrome 2 Metallic / Ceramic Coating 3 is applied to base 2 which gives the ring 1 properties of higher wear resistance, lower elastic modulus and, concomitantly, a considerable reduction in internal stress values, reducing the occurrence of cracks in the coating and the consequent scaling as compared to the prior art, particularly those using chromium nitride monolayer coatings.
Tal como é mencionado acima, o revestimento 3 compreende uma pluralidade de camadas Metálicas/Cerâmicas 5,5' à base cromo arranjadas de modo a formar uma periodicidade P. Logo, a periodicidade P compreende pelo menos duas camadas 5,5' adjacentes, obrigatoriamente de constituição diversa, isto é, uma camada 5 possui uma fase preponderante metálica e uma outra camada 5' possui uma fase preponderante cerâmica. Assim, o revestimento 3 terá pelo menos quatro camadas 5,5'.  As mentioned above, cladding 3 comprises a plurality of 5.5 'Chrome-based Metal / Ceramic layers arranged to form a P-periodicity. Therefore, P-periodicity comprises at least two adjacent 5.5' layers, which must be of different constitution, that is, one layer 5 has a preponderant metallic phase and another layer 5 'has a preponderant ceramic phase. Thus, the coating 3 will have at least four layers 5.5 '.
Uma das qualidades da camada metálica 5 que compõe o revestimento 3, compreende o cromo (Cr) na sua forma metálica (ilustrada como as camadas mais claras na figura 2), cuja principal característica mecânica é uma maior ductilidade, característica essa que facilita a acomoda- ção das duras camadas cerâmicas 5'.  One of the qualities of the metallic layer 5 that makes up the coating 3 comprises chromium (Cr) in its metallic form (illustrated as the lighter layers in figure 2), whose main mechanical characteristic is greater ductility, which facilitates the accommodation - 5 'hard ceramic layers.
Por sua vez, a camada cerâmica 5' compreende nitreto de cromo (ilustrada como as camadas mais escuras na figura 2), preferencialmente na forma de CrN (embora, evidentemente, possa haver um percentual reduzido de Cr2N e/ou de outros compostos/elementos em sua composição), tendo como principal característica mecânica a elevada dureza. É de especial importância notar que nitreto de cromo da camada cerâmica 5' também se pode apresentar predominantemente com a fase Cr2N ao invés da fase CrN. In turn, the ceramic layer 5 'comprises chromium nitride (shown as the darker layers in figure 2), preferably in the form of CrN (although, of course, there may be a reduced percentage of Cr 2 N and / or other compounds. / elements in its composition), having as its main mechanical characteristic the high hardness. It is of particular importance to note that 5 'ceramic layer chromium nitride may also present predominantly with the Cr 2 N phase rather than the CrN phase.
Por tudo o acima exposto, resta claro que a periodicidade P possui pelo menos uma camada metálica 5 composta preponderantemente por Cr e uma camada cerâmica 5' composta preponderantemente por CrN ou Cr2N. De modo preferível, tal como ilustrado na figura 2, a camada metálica 5 deve estar posicionada adjacentemente à camada cerâmica 5' ou vice-versa. Com isso, consegue-se garantir que as camadas de revestimento 5,5' estão intercaladas sem repetição. From all of the above, it is clear that the periodicity P has at least one metal layer 5 composed predominantly of Cr and one ceramic layer 5 'composed predominantly of CrN or Cr 2 N. Preferably, as shown in Figure 2, the metal layer 5 should be positioned adjacent to the ceramic layer 5 'or vice versa. This ensures that the 5.5 'coating layers are interspersed without repetition.
De realçar ainda que qualquer das camadas 5,5' pode ser depositada na superfície da base 2, sendo portanto possível depositar como primeira camada na base 2 tanto a camada metálica 5 quanto a camada cerâmica 5'. Naturalmente, após cada camada depositada se alternará uma camada distinta, ou seja, se a primeira camada a ser depositada na superfí- cie da base 2 for a camada cerâmica 5' seguir-se-á a camada metálica 5, ou vice-versa, e assim sucessivamente.  It is further noted that any of the 5,5 'layers may be deposited on the surface of the base 2, therefore it is possible to deposit as the first layer on the base 2 both the metallic layer 5 and the ceramic layer 5'. Of course, after each deposited layer a distinct layer will alternate, ie if the first layer to be deposited on the surface of the base 2 is the ceramic layer 5 'then the metallic layer 5 will be followed, or vice versa, and so on.
Alternativamente, pode-se conceber um anel 1 de acordo com os ensinamentos da presente invenção no qual pode haver, em regime de exceção, duas camadas de igual qualidade adjacentes, dependendo das qualidades de resistência e ductilidade que se deseja conferir ao revestimento 3.  Alternatively, a ring 1 may be designed according to the teachings of the present invention in which there may exceptionally be two adjacent layers of equal quality, depending on the strength and ductility qualities desired to be imparted to the coating 3.
Conforme pode ser claramente visto na figura 2, o revestimento 3 da concretização preferível do anel 1 compreende nove camadas metálicas/cerâmicas 5,5', onde as qualidades das camadas 5,5' do revestimento 3 estão intercaladas sem repetição.  As can be clearly seen from Figure 2, the coating 3 of the preferred embodiment of ring 1 comprises nine 5.5 'metal / ceramic layers, where the qualities of the 5.5' layers of coating 3 are interspersed without repetition.
Caso necessário ou desejável, as camadas 5,5' podem compreender um ou mais elementos químicos adicionais, em proporções variadas e calculadas em função da propriedade mecânica que se deseja alcançar. Mesmo ocorrendo alguma mistura nas camadas individuais 5,5', é esperado alcançar o mesmo grau de vantagens, isto é, são também esperadas as já referidas vantagens da presente invenção com um revestimento 3 multica- madas 5,5' onde uma camada tenha predominância cerâmica e a camada subsequente predominância metálica.  If necessary or desirable, the 5.5 'layers may comprise one or more additional chemical elements, in varying proportions and calculated as a function of the desired mechanical property. Even if some mixing occurs in the individual 5.5 'layers, it is expected to achieve the same degree of advantages, that is, the aforementioned advantages of the present invention with a 5.5' multilayer coating 3 where one layer has predominance are also expected. ceramic and the subsequent metallic predominance layer.
De igual modo, se esperam alcançar a mesmas vantagens caso se usem elementos similares para proporcionar um revestimento multica- madas metálicas/cerâmicas. Tais possíveis elementos químicos podem estar presentes em pelo menos uma das camadas 5,5', em algumas delas ou em todas, em função das propriedades mecânicas do revestimento que se deseja obter desde que mantidas as características de um revestimento mul- ticamadas metálicas/cerâmicas. Similarly, the same advantages are expected to be achieved if similar elements are used to provide a metal / ceramic multilayer coating. Such possible chemical elements may be present in at least one of the 5.5 'layers, some of them or in all, depending on the mechanical properties of the coating desired, provided that the characteristics of a metal / ceramic multi-layer coating are maintained.
Apresenta-se abaixo uma tabela comparativa referente às diver- sas propriedades alcançadas pela presente invenção e pelo estado da técnica.  Below is a comparative table referring to the various properties achieved by the present invention and the state of the art.
Revestimento/ Multicamadas Monocamada  Single Layer Coating / Multilayer
Resultados CrN/Cr CrN  CrN / Cr CrN results
Dureza 1350 HV 1200 HV  Hardness 1350 HV 1200 HV
Módulo de Young 200 MPa 250 MPa  Young 200 MPa 250 MPa Module
Estresse interno -310 N/mm2 -1100 N/mm2 Internal Stress -310 N / mm 2 -1100 N / mm 2
Teste riscamento 135 N 110 N  Scratch test 135 N 110 N
Como pode ser observado na tabela acima, o revestimento 3 da presente invenção obteve resultados realmente superiores em todas as características medidas. Confirma-se, portanto, um aumento dos valores para propriedades antagónicas, fato que realmente comprova o sucesso do revestimento 3 da presente invenção.  As can be seen from the table above, the coating 3 of the present invention obtained really superior results in all measured characteristics. Therefore, an increase in the values for antagonistic properties is confirmed, a fact which really proves the success of the coating 3 of the present invention.
Sendo assim, a presente invenção, quando comparada com o revestimento típico de monocamada CrN, alcança um valor para o modulo de elasticidade sensivelmente menor e uma expressiva redução do estresse interno (sensivelmente 3,5 vezes menor).  Thus, the present invention, when compared with the typical CrN monolayer coating, achieves a significantly lower value for the modulus of elasticity and a significant reduction in internal stress (substantially 3.5 times less).
Estes valores evidenciam que há um aumento da energia de adesão devido à redução do estresse interno e um aumento da energia e- lástica possibilitado pela redução do modulo de elasticidade.  These values show that there is an increase in adhesion energy due to the reduction of internal stress and an increase in elastic energy made possible by the reduction of the elastic modulus.
A figura 2 evidencia um revestimento 3 com duas camadas dis- tintas 5,5' onde a diferença se apresenta basicamente no conteúdo de cromo, sendo portanto esperadas fronteiras coesas entre as camadas Metálicas /Cerâmicas 5,5' de forma que a garantir a adesão entre as camadas 5,5' evitando-se assim a propagação de trincas na sua interface.  Figure 2 shows a coating 3 with two distinct 5.5 'layers where the difference is basically in the chromium content, therefore cohesive boundaries between the 5.5' Metallic / Ceramic layers are expected in order to ensure adhesion. between the 5,5 'layers thus avoiding the propagation of cracks in its interface.
Desse modo, com uso do revestimento 3 da presente invenção, a redução nos valores de estresse interno traduz-se em uma resistência muito maior ao fenómeno de escamação, no qual pequenas porções do re- vestimento são desplacadas devido à ocorrência de microtrincas provocadas pelo acúmulo de tensões e pela baixa ductilidade. O grande inconveniente técnico estrutural é que a escamação tende a ocorrer em determinadas partes do anel, enquanto em outras partes o revestimento permanece intacto ou pouco danificado mesmo ao final da vida útil da peça. Thus, by using the coating 3 of the present invention, the reduction in internal stress values translates into a much greater resistance to the scaling phenomenon, in which small portions of the The dressings are bare due to the occurrence of microcracks caused by the accumulation of tensions and low ductility. The major technical drawback is that scaling tends to occur in certain parts of the ring, while in other parts the coating remains intact or undamaged even at the end of part life.
Essa redução nos valores de estresse interno traz a reboque as vantagens de possibilitar um aumento na energia de adesão das camadas entre si com consequente redução da espessura do revestimento, possível uma vez que se consegue uma grande redução da escamação garantindo- se que, mesmo com uma espessura reduzida, haverá revestimento 3 durante toda a vida operacional do anel.  This reduction in internal stress values brings the advantages of allowing an increase in the adhesion energy of the layers with each other with consequent reduction of the coating thickness, which is possible since a great reduction of the scaling is achieved, ensuring that even with At a reduced thickness, there will be coating 3 for the entire operating life of the ring.
Por sua vez, os resultados alcançados no teste de riscamento ("Scratch Test') são também, no caso da presente invenção, substancialmente superiores, revelando que o revestimento 3 multicamadas CrN/Cr a- presenta maior tenacidade que o revestimento do estado da técnica (revestimento monocamada Cr), contribuindo de modo efetivo para uma maior resistência à delaminação do recobrimento.  In turn, the results achieved in the Scratch Test are also substantially higher in the case of the present invention, revealing that the CrN / Cr multilayer coating 3 has higher toughness than the prior art coating. (Cr monolayer coating), effectively contributing to greater resistance to coating delamination.
É, portanto, evidente que o revestimento 3 multicamadas Metálica/Cerâmica 5,5' da presente invenção, de estrutura preferencial de cromo metálico e nitreto de cromo (na fase CrN ou Cr2N), proporciona uma evidente melhora no compromisso entre uma maior capacidade de absorver o estresse concomitantemente com uma maior resistência à propagação superficial de trincas devido às melhores características de resistência ao estresse no cisalhamento externo, fato que resulta em uma performance superior do revestimento 3 da presente invenção para anéis de pistão 1 no que diz respeito à aderência coesiva (resistência à delaminação). It is therefore evident that the 5.5 'Multilayer Metal / Ceramic coating 3 of the present invention, of preferred chrome metal and chromium nitride structure (in the CrN or Cr 2 N phase), provides a clear improvement in the compromise between higher the ability to absorb stress concomitantly with greater resistance to surface crack propagation due to improved external shear stress resistance characteristics, which results in superior performance of the coating 3 of the present invention for piston rings 1 with respect to cohesive adhesion (delamination resistance).
O processo de deposição aplicado na presente invenção é um processo de deposição física de vapor (PVD), preferivelmente por arco catódico, ou Arco-PVD que é uma técnica de PVD onde um arco elétrico é u- sado para vaporizar material de um catodo-alvo. O material vaporizado então condensa sobre um substrato e forma um filme fino.  The deposition process applied in the present invention is a physical vapor deposition (PVD) process, preferably by cathode arc, or PV-Arc which is a PVD technique where an electric arc is used to vaporize material from a cathode. target. The vaporized material then condenses on a substrate and forms a thin film.
Em essência, o controle da pressão do gás (por exemplo, nitro- génio) utilizado possibilita a produção das camadas 5,5' sequencialmente, sendo que as camadas compostas por nitreto de cromo têm um percentual de átomos de Nitrogénio entre 22% e 25% em peso, ao passo que nas camadas compostas por cromo metálico possuem substancialmente 0% de átomos de Nitrogénio. Para evitar a interferência dos diferentes níveis de nitrogénio em cada camada 5,5', são aplicadas elevadas velocidades de bombardeamento através de turbo bombas. In essence, gas pressure control (eg nitro- used) enables the production of the 5.5 'layers sequentially, with the chromium nitride layers having a percentage of nitrogen atoms of between 22% and 25% by weight, whereas in the chromium metal layers they have substantially 0% Nitrogen atoms. To avoid interference of different nitrogen levels in each 5.5 'layer, high bombardment rates are applied through turbo pumps.
Os valores de espessura e periodicidade são considerados bastante estáveis por todo o revestimento (vide figura 2), no entanto, as cama- das 5,5' acompanham as deformidades da base 2, resultando nas formas visíveis da figura 2.  The thickness and periodicity values are considered quite stable throughout the coating (see figure 2), however, the 5.5 'layers follow the base 2 deformities, resulting in the visible shapes of figure 2.
No caso do revestimento 3 da presente invenção, a maior dureza é obtida com a composição de nitreto de cromo e a maior ductilidade, por sua vez, é conseguida com o uso de cromo metálico. A combinação dessas duas composições na forma das camadas 5,5', tal como mencionado acima, traz vantagens surpreendentes, notadamente no benefício apresentado ao revestimento 3 como um todo pela sua maior capacidade de absorção de estresse interno. As camadas 5 de cromo metálico, mais dúcteis, absorvem os esforços e deformam, diminuindo assim as forças de deformação às quais as camadas 5' mais rígidas de nitreto de cromo são submetidas, proporcionando uma menor tendência ao aparecimento de microtrincas nestas. O resultado é um incremento considerável no desempenho do anel 1.  In the case of the coating 3 of the present invention, the highest hardness is obtained with the chromium nitride composition and the highest ductility is achieved with the use of metal chromium. The combination of these two compositions in the form of the 5,5 'layers, as mentioned above, brings surprising advantages, notably in the benefit presented to the coating 3 as a whole for its greater internal stress absorption capacity. The more ductile metallic chrome layers 5 absorb stress and deform, thereby decreasing the deformation forces to which the stiffer chrome nitride 5 'layers are subjected, providing a lower tendency for microcracks to appear on them. The result is a considerable increase in ring performance 1.
Ainda, pelo fato de que as camadas metálicas 5 dúcteis de cromo permitem uma melhor acomodação das camadas cerâmicas 5 mais du- ras de nitreto de cromo, ocorre uma redução da espessura do revestimento 3 sem prejuízo na resistência ao desgaste.  In addition, because the ductile chrome metal layers 5 allow better accommodation of the longer ceramic chrome nitride layers 5, there is a reduction in the thickness of the coating 3 without impairing wear resistance.
A concretização preferível do anel 1 , ilustrada na figura 2, apresenta uma dureza superficial da ordem de 1000 a 2.000 HV, sendo preferivelmente em torno de 1350 HV, com um estresse interno de cerca de -310 N/mm2. De modo preferível, a espessura do revestimento (3) apresenta valores na faixa de cerca de substancialmente 10 a 60 mícrons, ou seja, apresenta espessura muito reduzida (ηΒηοΙθγβή. Opcionalmente, pode ser provida uma camada de adesão composta por cromo, níquel ou cobalto posicionada entre a base 2 e o revestimento 3. The preferred embodiment of ring 1, illustrated in Figure 2, has a surface hardness of the order of 1000 to 2000 HV, preferably around 1350 HV, with an internal stress of about -310 N / mm 2 . Preferably, the thickness of the coating (3) is in the range of about 10 to 60 microns, i.e. very low thickness (ηΒηοΙθγβή. Optionally, an adhesion layer composed of chromium, nickel or cobalt may be provided positioned between base 2 and coating 3.
Preferivelmente, o revestimento 3 é aplicado por toda a superfí- cie externa do anel 1 , mas nada impede que seja aplicado em partes determinadas, removido parcialmente ou ainda que, por sobre ele, aplique-se outra qualidade de revestimento qualquer. Um anel de pistão assim configurado continua incluído no escopo de proteção das reivindicações.  Preferably, the coating 3 is applied over the entire outer surface of ring 1, but nothing prevents it from being applied in certain parts, partially removed or any other coating quality applied thereon. A piston ring thus configured remains within the protection scope of the claims.
Tendo sido descrito exemplos de concretização preferidos, deve ser entendido que o escopo da presente invenção abrange outras possíveis variações, sendo limitado tão-somente pelo teor das reivindicações apensas, aí incluídos os possíveis equivalentes.  Having described preferred embodiments, it should be understood that the scope of the present invention encompasses other possible variations, being limited only by the content of the appended claims, including the possible equivalents thereof.

Claims

REIVINDICAÇÕES
1. Anel de pistão, particularmente idealizado para utilização em motores de combustão interna ou compressores, compreendendo pelo menos uma base (2) metálica à qual é aplicado, pelo processo de deposição física de vapor (PVD), um revestimento (3) que compreende uma periodicidade (P), formada por pelo menos uma primeira camada (5) e pelo menos uma segunda camada (5') adjacentes, caracterizado pelo fato de que a primeira camada (5) é formada preponderantemente por cromo metálico (5) e a segunda camada é formada preponderantemente por cromo cerâmico (5'). 1. Piston ring, particularly designed for use in internal combustion engines or compressors, comprising at least one metallic base (2) to which is applied, by the physical vapor deposition (PVD) process, a coating (3) comprising a periodicity (P), formed by at least one first layer (5) and at least one second layer (5') adjacent, characterized by the fact that the first layer (5) is formed preponderantly by metallic chromium (5) and the The second layer is predominantly formed by ceramic chrome (5').
2. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que a periodicidade é composta por somente duas camadas adjacentes (5,5'), onde a primeira camada (5) é formada preponderantemente por cromo metálico (5) e a segunda camada é formada preponderantemente por cromo cerâmico (5'). 2. Ring according to claim 1, characterized by the fact that the periodicity is composed of only two adjacent layers (5,5'), where the first layer (5) is formed predominantly by metallic chromium (5) and the second layer is predominantly formed by ceramic chrome (5').
3. Anel de acordo com a reivindicação 1 ou 2, caracterizado pelo fato de que as primeira e segunda camadas (5,5') contêm um elemento químico adicional selecionado dentre o grupo constituído por Oxigénio ou Carbono em um percentual não superior a 10% em massa. 3. Ring according to claim 1 or 2, characterized by the fact that the first and second layers (5,5') contain an additional chemical element selected from the group consisting of Oxygen or Carbon in a percentage not exceeding 10% in large scale.
4. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que a dureza Vickers do revestimento apresenta valores entre 1.000 e 4. Ring according to claim 1, characterized by the fact that the Vickers hardness of the coating has values between 1,000 and
2.000 HV. 2,000 HV.
5. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que a espessura do revestimento (3) apresenta valores na faixa de 10 a 60 mícrons. 5. Ring according to claim 1, characterized by the fact that the thickness of the coating (3) has values in the range of 10 to 60 microns.
6. Anel de acordo com a reivindicação 5, caracterizado pelo fato de que o revestimento (3) é nanolayer. 6. Ring according to claim 5, characterized by the fact that the coating (3) is a nanolayer.
7. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que a base (2) é composta por aço com 10% a 17% de Cromo. 7. Ring according to claim 1, characterized by the fact that the base (2) is composed of steel with 10% to 17% chromium.
8. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que a base (2) é composta por ferro fundido. 8. Ring according to claim 1, characterized by the fact that the base (2) is composed of cast iron.
9. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que o cromo cerâmico que constitui a segunda camada (5') é preferível- mente nitreto de cromo (CrN) e essa segundas camada possui um percentual de Nitrogénio, em peso, entre 11% e 17%. 9. Ring according to claim 1, characterized by the fact that the ceramic chrome constituting the second layer (5') is preferable - chromium nitride (CrN) and this second layer has a percentage of Nitrogen, by weight, between 11% and 17%.
10. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que a camada de nitreto de cromo (5') pode apresentar fase CrN ou Cr2N. 10. Ring according to claim 1, characterized by the fact that the chromium nitride layer (5') may have a CrN or Cr 2 N phase.
11. Anel de acordo com a reivindicação 1 , caracterizado pelo fato de que é provida uma camada de adesão composta por cromo, níquel ou cobalto posicionada entre a base (2) e o revestimento (3). 11. Ring according to claim 1, characterized by the fact that an adhesion layer composed of chromium, nickel or cobalt is provided positioned between the base (2) and the coating (3).
PCT/BR2010/000428 2009-12-21 2010-12-21 Piston ring WO2011075804A1 (en)

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CN102869906A (en) 2013-01-09
BRPI0905186A2 (en) 2011-08-09

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